CN105481363B - A kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic - Google Patents
A kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic Download PDFInfo
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- CN105481363B CN105481363B CN201510998609.7A CN201510998609A CN105481363B CN 105481363 B CN105481363 B CN 105481363B CN 201510998609 A CN201510998609 A CN 201510998609A CN 105481363 B CN105481363 B CN 105481363B
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Abstract
The preparation method of a kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, which is characterized in that formula components include zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide Co2O3, silica SiO2, nitre silver oxide Ag2O, gallium nitrate Ga (NO3)3, yttrium nitrate Y (NO3)3.Advantage is：Leakage current is inhibited；The common addition of Y and Ga elements makes the ageing properties of the ZnO varistor of this formula making more stablize, and eliminates the shortcoming that the next leakage current of simple addition Ag ion bands cannot inhibit.
Description
Technical field
The present invention relates to technical field of material chemistry, especially a kind of ceramics and preparation method thereof.
Background technology
ZnO varistor be using ZnO as primary raw material, add a small amount of Bi2O3, Sb2O3, MnO2, Cr2O3, Co2O3,
Auxiliary ingredients are used as with silver glass powder etc., are prepared using ceramic sintering process.Due to its good non-linear behaviour and greatly
The advantages of discharge capacity, since 19 century 70s are found, core member of the ZnO varistor as electric system arrester
Part is widely used in the overvoltage protection of electric system lightning protection and power equipment.
Especially it is extra-high voltage system with the continuous improvement of transmission voltage grade, apparatus insulated problem becomes increasingly conspicuous, entirely
Face raising will be apparatus insulated to pay through the nose.The arrester assembled using the ZnO varistor of high gradient, low residual voltage
The dielectric level that system can be reduced reduces the weight and volume of power transmission and transforming equipment, improves the reliability of transmission system.
The nonlinear characteristic of ZnO varistor can be divided into three regions：Low current area, middle Current Zone and high current area.
Low current area (<It 10-4A/cm2) is also known as prebreakdown area, crystal boundary shows high-impedance state in the region, and I-V curve shows as Europe
Nurse characteristic, the Ohm characteristic slope of curve in the region is bigger, then the power dissipation characteristics in leakage current region of ZnO varistor is more stable, pressure-sensitive electricity
Press U1mA also higher.Middle Current Zone is nonlinear resistance area, this zone current increased dramatically and voltage increases slow, this area
Domain I-V characteristic is determined by ZnO crystal grain with ZnO crystal boundaries joint effect, is the workspace of varistor.High current area (>103A/
Cm2) and become Ohm characteristic, the resistance of region ZnO crystal grain determines the height of residual voltage, while the region is flat in I-V characteristic
The position that face occurs, determines the size of ZnO varistor discharge capacity.
Whether in middle Current Zone or high current area, ZnO grain resistances all affect I-V characteristic.It is pressure-sensitive to reduce ZnO
The residual voltage of resistance, it is necessary to reduce the resistivity of ZnO varistor.According to it is previous studies have shown that add a certain amount of alms giver from
Son can significantly improve the resistivity of ZnO crystal grain, to achieve the purpose that reduce residual voltage.It is adopted mostly in actual industrial production
Al ions are used to be added in ZnO varistor material as donor ion, but the addition of Al ions is usually associated with leakage electricity
The increase of stream, also results in the reduction of nonlinear factor, and the aging characteristics of ZnO varistor also become unstable.It is answered in industry
In, also have in such a way that ZnO and part adjunct are pre-sintered so that part mixed raw material pre-reaction, to improve pressure
The potential barrier and stability of quick material, this mode make production technology complicate.Mainly pass through the uniform journey of raising crystal grain at present
Degree so that electric current can uniform flow entire varistor valve, to improve the discharge capacity of ZnO varistor, but it is brilliant
The uniformity coefficient of grain is affected by sintering process and raw material mixed grinding technique etc., accomplishes that the homogenization of crystal grain is difficult
It is larger.
Invention content
The purpose of the present invention is to solve the above problem, a kind of big discharge capacity, low residual voltage, high gradient oxidation are devised
The preparation method of zinc based varistor.Specifically design scheme is：
A kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, which is characterized in that formula components packet
Include zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide
Co2O3, silica SiO2, nitre silver oxide Ag2O, gallium nitrate Ga (NO3)3, yttrium nitrate Y (NO3)3。
Molar ratio between each formula components is：
ZnO：Bi2O3：Sb2O3：MnO2：Cr2O3：Co2O3：SiO2：Ag2O：Ga(NO3)3： Y(NO3)3=87.5~95.8:
0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2. 0:0.1-1.0:0.1-1.0：1.0-1.5.
The preparation method of a kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, preparation process include
Prepare auxiliary addition slurry, molding, sintering, it includes first ball milling, secondary ball milling, three times that preparations auxiliary, which adds sauce step,
It is ball milling, mist projection granulating, automatic aqueous.
In the first ball milling step, the ingredient of the first ball milling includes Bi2O3、MnO2、Sb2O3、 Co2O3、SiO2、
Cr2O3, deionized water, the first Ball-milling Time is more than 6h, obtains first ball milling auxiliary mixed slurry,
The Bi being added2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient is:0.5-2.0:0.5-1.5:0.5-
1.0:0.5-1.0:0.5-1.5:1.0-2.0。
The forming step is compression molding will be dried using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm
Particulate material compression molding after granulation, briquetting pressure 150MPa, molding time 3min.
The sintering step is completed using high temperature circuit, and in the sintering step, temperature control is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
From 400 DEG C to 1000 DEG C, heating-up time 3h；
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h；
3h is kept the temperature at 1200 DEG C；
Temperature fall；
In secondary ball milling step, into the first ball milling auxiliary mixed slurry, addition ZnO, PVAC polyvinylalcohol, powder dissipate
Agent, deionized water, and ball milling mixing obtain secondary ball milling and assist mixed slurry, the addition ZnO and first ball to being uniformly dispersed
Bi in mill auxiliary mixed slurry2O3Molar ratio be 87.5~95.8：0.5-2.0.
Three times in ball milling step, assist that Ag is added in mixed slurry to the secondary ball milling2O： Ga(NO3)3：Y(NO3)3、
Ball milling three times is carried out after deionized water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga(NO3)3：
Y(NO3)3It is 0.1-1.0 to assist the molar ratio for the ZnO being added in mixed slurry with secondary ball milling:0.1-1.0：0.5~1.5：
87.5~95.8.
Big discharge capacity that above-mentioned technical proposal through the invention obtains, low residual voltage, high gradient Zinc-oxide piezoresistor
Ceramics and preparation method thereof, advantage are：
It is added to Ag and Y element simultaneously in ZnO and mixed slurry, the collective effect of Ag and Y-ion makes high current area
Grain resistance decline, the residual voltage for reducing ZnO varistor is horizontal；On V-I characteristic curves, the inflection point in high current area is right
It moves, improves the ZnO varistors that this formula makes and release the ability of charge；Under the collective effect of Y and Ga ions so that this
It is formulated V-I characteristic of the ZnO varistor made in low current area more to stablize, voltage gradient is improved, nonlinear factor
Increase, compared with addition Ag ions merely, leakage current is inhibited；The common addition of Y and Ga elements is so that this formula makes
The ageing properties of ZnO varistor more stablize, eliminating the leakage current that simple addition Ag ion bands come cannot inhibit
Shortcoming.
Specific implementation mode
A kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, which is characterized in that formula components packet
Include zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide
Co2O3, silica SiO2, nitre silver oxide Ag2O, gallium nitrate Ga (NO3)3, yttrium nitrate Y (NO3)3。
Molar ratio between each formula components is：
ZnO：Bi2O3：Sb2O3：MnO2：Cr2O3：Co2O3：SiO2：Ag2O：Ga(NO3)3： Y(NO3)3=87.5~95.8:
0.5-2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2. 0:0.1-1.0:0.1-1.0：1.0-1.5.
The preparation method of a kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, preparation process include
Prepare auxiliary addition slurry, molding, sintering, it includes first ball milling, secondary ball milling, three times that preparations auxiliary, which adds sauce step,
It is ball milling, mist projection granulating, automatic aqueous.
In the first ball milling step, the ingredient of the first ball milling includes Bi2O3、MnO2、Sb2O3、 Co2O3、SiO2、
Cr2O3, deionized water, the first Ball-milling Time is more than 6h, obtains first ball milling auxiliary mixed slurry,
The Bi being added2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient is:0.5-2.0:0.5-1.5:0.5-
1.0:0.5-1.0:0.5-1.5:1.0-2.0。
The forming step is compression molding will be dried using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm
Particulate material compression molding after granulation, briquetting pressure 150MPa, molding time 3min.
The sintering step is completed using high temperature circuit, and in the sintering step, temperature control is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
From 400 DEG C to 1000 DEG C, heating-up time 3h；
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h；
3h is kept the temperature at 1200 DEG C；
Temperature fall；
In secondary ball milling step, into the first ball milling auxiliary mixed slurry, addition ZnO, PVAC polyvinylalcohol, powder dissipate
Agent, deionized water, and ball milling mixing obtain secondary ball milling and assist mixed slurry, the addition ZnO and first ball to being uniformly dispersed
Bi in mill auxiliary mixed slurry2O3Molar ratio be 87.5~95.8：0.5-2.0.
Three times in ball milling step, assist that Ag is added in mixed slurry to the secondary ball milling2O： Ga(NO3)3：Y(NO3)3、
Ball milling three times is carried out after deionized water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga(NO3)3：
Y(NO3)3It is 0.1-1.0 to assist the molar ratio for the ZnO being added in mixed slurry with secondary ball milling:0.1-1.0：0.5~1.5：
87.5~95.8.
Embodiment one
According to a kind of big discharge capacity of system for ultra-high voltage transmission, the low residual voltage oxygen of patent specification introduction of the present invention
Change the preparation method of zinc based varistor, carries out the practical preparation of high-performance ZnO based varistor.
(1) raw material is prepared：
ZnO (87.5%), Bi in the following proportions2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%),
Cr2O3(1.0mol%), Co2O3(1.5mol%), SiO2(2.0mol%) and Ag2O (1.0mol%), Ga (NO3)3
(1.0mol%), Y (NO3)3(1.5mol%) prepares initial feed.
(2) prepared by slurry
1) ball milling adjunct：
By Bi2O3(2.0mol%), Sb2O3(1.5mol%), MnO2(1.0mol%), Cr2O3(1.0mol%), Co2O3
(1.5mol%), SiO2(2.0mol%) is put into the ball grinder of planetary ball mill, and suitable deionized water, ball milling is added
8 hours.
2) ZnO of (87.5mol%) is added in auxiliary mixed slurry after ball milling, adds PVA, dispersant and suitable
Deionized water, by all mixed raw material mixing and ball millings until being uniformly dispersed.
3) addition silver, aluminium plus gallium ion
In uniformly mixed ZnO and adjunct, Ag is added2O (1.0mol%), Ga (NO3)3(1.0mol%), Y
(NO3)3(1.5mol%), continues ball milling 2 hours, aqueous after mist projection granulating.
(3) it is molded
The powder obtained in previous step is sprayed, it is automatic it is aqueous after, using tabletting molding process.Use hydraulic pressure tabletting
The cylindrical die of machine and diameter 50mm, by the particulate material compression molding after drying-granulating, briquetting pressure 150MPa, pressurize
3 minutes time.
(4) it is sintered
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere：
From room temperature to 400 DEG C, 2 hours heating-up times；
Dumping 4 hours are kept the temperature at 400 DEG C；
From 400 DEG C to 1000 DEG C, 3 hours heating-up times；
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times；
3 hours are kept the temperature at 1200 DEG C；
Temperature fall.
Properties test is carried out to the sample for the ZnO varistor being prepared.Its residual voltage ratio is 1.47,2ms square waves
Discharge capacity reaches 535J/cm3, breakdown voltage gradient mean value 440V/mm, in addition to this, leakage current are less than 1 μ A/cm2, non-
Linear coefficient is more than 70.Its performance has met commercial Application requirement.
Embodiment two
According to a kind of big discharge capacity of system for ultra-high voltage transmission, the low residual voltage oxygen of patent specification introduction of the present invention
Change the preparation method of zinc based varistor, carries out the practical preparation of high-performance ZnO based varistor.
(1) raw material is prepared：
ZnO (95.8mol%), Bi in the following proportions2O3(0.5mol%), Sb2O3(0.5mol%), MnO2
(0.5mol%), Cr2O3(0.5mol%), Co2O3(0.5mol%), SiO2(1.0mol%) and Ag2O (0.1mol%),
Ga(NO3)3(0.1mol%), Y (NO3)3(0.5mol%) prepares initial feed.
(2) prepared by slurry
1) ball milling adjunct：
By Bi2O3(0.5mol%), Sb2O3(0.5mol%), MnO2(0.5mol%), Cr2O3(0.5mol%), Co2O3
(0.5mol%), SiO2(1.0mol%) is put into the ball grinder of planetary ball mill, and suitable deionized water, ball milling is added
6 more than hour.
2) in auxiliary mixed slurry after ball milling be added (87.5~95.8mol%) ZnO, add PVA, dispersant and
Suitable deionized water, by all mixed raw material mixing and ball millings until being uniformly dispersed.
3) addition silver, aluminium plus gallium ion
In uniformly mixed ZnO and adjunct, Ag is added2O (0.1~1.0mol%), Ga (NO3)3(0.1~
1.0mol%), Y (NO3)3(0.5~1.5mol%), continues ball milling 2 hours, aqueous after mist projection granulating.
(3) it is molded
The powder obtained in previous step is sprayed, it is automatic it is aqueous after, using tabletting molding process.Use hydraulic pressure tabletting
The cylindrical die of machine and diameter 50mm, by the particulate material compression molding after drying-granulating, briquetting pressure 150MPa, pressurize
3 minutes time.
(4) it is sintered
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere：
From room temperature to 400 DEG C, 2 hours heating-up times；
Dumping 4 hours are kept the temperature at 400 DEG C；
From 400 DEG C to 1000 DEG C, 3 hours heating-up times；
From 1000 DEG C to 1200 DEG C, 1.5 hours heating-up times；
3 hours are kept the temperature at 1200 DEG C；
Temperature fall.
Properties test is carried out to the sample for the ZnO varistor being prepared.Its residual voltage ratio is 1.49,2ms square waves
Discharge capacity reaches 508J/cm3, breakdown voltage gradient mean value 463V/mm, in addition to this, leakage current are less than 1 μ A/cm2, non-thread
Property coefficient is more than 70.Its performance has met commercial Application requirement.
Above-mentioned technical proposal only embodies the optimal technical scheme of technical solution of the present invention, those skilled in the art
The principle of the present invention is embodied to some variations that some of which part may be made, belongs to the scope of protection of the present invention it
It is interior.
Claims (5)
1. a kind of big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic, which is characterized in that formula components include
Zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese dioxide MnO2, chromium oxide Cr2O3, cobalt sesquioxide Co2O3、
Silica SiO2, silver oxide Ag2O, gallium nitrate Ga (NO3)3, yttrium nitrate Y (NO3)3,
Molar ratio between each formula components is：
ZnO：Bi2O3：Sb2O3：MnO2：Cr2O3：Co2O3：SiO2：Ag2O：Ga(NO3)3：Y(NO3)3=87.5-95.8:0.5-
2.0:0.5-1.5:0.5-1.0:0.5-1.0:0.5-1.5:1.0-2.0:0.1-1.0:0.1-1.0：1.0-1.5
Preparation process includes preparing auxiliary addition slurry, molding, sintering, and the preparation auxiliary addition slurry stage includes first
Ball milling, secondary ball milling, three times ball milling, mist projection granulating, automatic aqueous, in the first ball milling step, the first ball milling at
It includes Bi to divide2O3、MnO2、Sb2O3、Co2O3、SiO2、Cr2O3, deionized water, the first Ball-milling Time is more than 6h, obtains first
Ball milling assists mixed slurry,
The Bi being added2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2The molar ratio of ingredient is:0.5-2.0:0.5-1.5:0.5-
1.0:0.5-1.0:0.5-1.5:1.0-2.0。
2. according to big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic described in claim 1, feature
It is, the forming step is compression molding, using hydraulic pressure tablet press machine and the cylindrical die of diameter 50mm, by drying-granulating
Particulate material compression molding afterwards, briquetting pressure 150MPa, molding time 3min.
3. according to big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic described in claim 1, feature
It is, the sintering step is completed using high temperature circuit, in the sintering step, temperature control is with time control：
From room temperature to 400 DEG C, heating-up time 2h；
Dumping 4h is kept the temperature at 400 DEG C；
From 400 DEG C to 1000 DEG C, heating-up time 3h；
From 1000 DEG C to 1200 DEG C, heating-up time 1.5h；
3h is kept the temperature at 1200 DEG C；
Temperature fall.
4. according to big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic described in claim 1, feature
It is, in secondary ball milling step, ZnO is added into the first ball milling auxiliary mixed slurry, PVAC polyvinylalcohol, pulvis, goes
Ionized water, and ball milling mixing obtains secondary ball milling and assists mixed slurry, the addition ZnO and first ball milling are auxiliary to being uniformly dispersed
Help Bi in mixed slurry2O3Molar ratio be 87.5-95.8：0.5-2.0.
5. according to big discharge capacity, low residual voltage, high gradient zinc oxide piezoresistor ceramic described in claim 4, feature
It is, three times in ball milling step, assists that Ag is added in mixed slurry to the secondary ball milling2O：Ga(NO3)3：Y(NO3)3, go from
Ball milling three times is carried out after sub- water, the time of the ball milling three times is 2h, obtains slurry, the addition Ag2O：Ga(NO3)3：Y
(NO3)3It is 0.1-1.0 to assist the molar ratio for the ZnO being added in mixed slurry with secondary ball milling:0.1-1.0：0.5-1.5：87.5-
95.8。
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